Mechanism of Preferential Adsorption of SO2 into Two Microporous Paddle Wheel Frameworks M(bdc)(ted)0.5
| العنوان: | Mechanism of Preferential Adsorption of SO2 into Two Microporous Paddle Wheel Frameworks M(bdc)(ted)0.5 |
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| المؤلفون: | Timo Thonhauser, Allison Dyevoich, Daniel H. Johnson, Kui Tan, Yves J. Chabal, Jing Li, Praveen K. Thallapally, Jian Liu, Pieremanuele Canepa, Qihan Gong |
| المصدر: | Chemistry of Materials. 25:4653-4662 |
| بيانات النشر: | American Chemical Society (ACS), 2013. |
| سنة النشر: | 2013 |
| مصطلحات موضوعية: | Condensed Matter - Materials Science, Materials science, Hydrogen bond, General Chemical Engineering, Ab initio, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Infrared spectroscopy, General Chemistry, chemistry.chemical_compound, symbols.namesake, Crystallography, chemistry, Molecular vibration, Materials Chemistry, symbols, Molecule, Density functional theory, Carboxylate, van der Waals force |
| الوصف: | The selective adsorption of a corrosive gas, SO$_2$, into two microporous pillared paddle-wheel frameworks M(bdc)(ted)0.5 [M = Ni, Zn; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine] is studied by volumetric adsorption measurements and a combination of in-situ infrared spectroscopy and ab initio density functional theory (DFT) calculations. The uptake of SO$_2$ in M(bdc)(ted)0.5 at room temperature is quite significant, 9.97 mol/kg at 1.13 bar. The major adsorbed SO$_2$ molecules contributing to the isotherm measurements are characterized by stretching bands at 1326 and 1144 cm$^{-1}$. Theoretical calculations including van der Waals interactions (based on vdW-DF) suggest that two adsorption configurations are possible for these SO$_2$ molecules. One geometry involves an SO$_2$ molecule bonded through its sulfur atom to the oxygen atom of the paddle-wheel building unit and its two oxygen atoms to the C-H groups of the organic linkers by formation of hydrogen bonds. Such a configuration results in a distortion of the benzene rings, which is consistent with the experimentally observed shift of the ring deformation mode. In the other geometry, SO$_2$ establishes hydrogen bonding with -CH$_2$ group of the ted linker through its two oxygen atoms simultaneously. The vdW-DF-simulated frequency shifts of the SO$_2$ stretching bands in these two configurations are similar and in good agreement with spectroscopically measured values of physisorbed SO$_2$.In addition, the IR spectra reveal the presence of another minor species, characterized by stretching modes at 1242 and 1105 cm$^{-1}$ and causing significant perturbations of MOFs vibrational modes (CH$_x$ and carboxylate groups). This species is more strongly bound, requiring a higher temperature ($\sim$150 $^\circ$C) to remove it than for the main physisorbed species. |
| تدمد: | 1520-5002 0897-4756 |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::4e01d578b048b1033bdc0b2c12cb9961Test https://doi.org/10.1021/cm401270bTest |
| حقوق: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....4e01d578b048b1033bdc0b2c12cb9961 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15205002 08974756 |
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